Vinyl alcohol polymer and cement slurry comprising same

ABSTRACT

Provided is a vinyl alcohol polymer having good fluid loss reducing performance. The vinyl alcohol polymer is a saponified product of a copolymer of a vinyl ester monomer and a multifunctional monomer, and has a degree of saponification of 70 to 95 mol % and a viscosity-average degree of polymerization of 1000 to 10000.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of PCT/JP2019/003766, filed Feb. 4,2019, which claims priority from JP 2018-029581, filed Feb. 22, 2018,the contents of which applications are incorporated herein by referencein their entireties for all purposes

TECHNICAL FIELD

The present invention relates to an additive for oil well cement,containing a vinyl alcohol polymer. The present invention also relatesto a cement slurry using the additive for oil well cement.

BACKGROUND ART

The oil well cement used in cementing of an oil well, a gas well, asteam well for geothermal power generation, and the like is filled intoa gap between a steel pipe and a well to protect the steel pipe(casing). Loss of contained water from a cement slurry due to highpressure at the time of injection and geothermal heat is typicallyreferred to as “fluid loss.” Fluid loss impairs the fluidity of thecement slurry and the strength after curing, and hence a fluid lossreducing agent is usually added to the cement slurry.

As an example of the fluid loss reducing agent, use of polyvinyl alcohol(hereinafter also referred to as “PVA”) is known. In recent years, asshale gas wells have particularly been mined deeper, the pressure andthe temperature conditions have become more stringent, and the amount ofthe fluid loss reducing agent added has been increased correspondingly.

However, due to a decrease in fluidity caused by thickening of thecement slurry and an increase in cost, improvement in fluid lossreducing the performance of the fluid loss reducing agent is required.

CITATION LIST Patent Literature

Patent Literature 1: International Publication No. WO2007/146348

Patent Literature 2: Japanese Patent Laid-Open No. 2015-196733

SUMMARY OF INVENTION Technical Problem

Patent Literatures 1 and 2 each disclose PVA used in the fluid lossreducing agent. Actually, these fluid loss reducing agents containingPVA do not realize the fluid loss reducing performance required for thecement slurry injected under high temperature and high pressure.

Thus, the main object of the present invention is to provide an additivefor oil well cement, containing a vinyl alcohol polymer, the additivehaving good fluid loss reducing performance.

Solution to Problem

That is, the present invention provides an additive for oil well cement,comprising a vinyl alcohol polymer, wherein the vinyl alcohol polymer isa saponified product of a copolymer of a vinyl ester monomer and amultifunctional monomer, and has a degree of saponification of 70 to 95mol % and a viscosity-average degree of polymerization of 1000 to 10000.

The multifunctional monomer may have a carbonyl group or an amide group.

The multifunctional monomer may be triallyl isocyanurate.

A structural unit derived from the multifunctional monomer in the vinylalcohol polymer may be 0.001 to 1.0 mol % per 100 mol % of a structuralunit derived from the vinyl ester monomer.

The content of the vinyl alcohol polymer having a particle size of 75 μmor less may be 30 mass % or less, and/or the content of the vinylalcohol polymer having a particle size of 500 μm or more may be 10 mass% or less.

The present invention provides a cement slurry comprising 0.01 to 30%bwoc of the additive for oil well cement.

Advantageous Effects of Invention

According to the present invention, an additive for oil well cement,containing a vinyl alcohol polymer, the additive having good fluid lossreducing performance, is provided.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the embodiments of the present invention will be describedin detail. However, the present invention is not limited to theembodiments described below.

The additive for oil well cement according to one embodiment of thepresent invention is preferable as an additive for the oil well cementused in cementing an oil well, a gas well, a steam well for geothermalpower generation, or the like. The additive for oil well cement of thepresent embodiment comprises a vinyl alcohol polymer that is obtained bycopolymerization of a vinyl ester monomer and a multifunctional monomerand in which the degree of saponification and the viscosity-averagedegree of polymerization are controlled.

The process of “cementing” in drilling of a well refers to an operationof injecting cement into a gap between a drilled well and a steel pipeinserted to the well. The cementing widely employs a method in whichcement and various additives are mixed in a dried state and then themixture is pumped while being slurried with high-pressure water. When avinyl alcohol polymer is used as a fluid loss reducing agent amongadditives, loss of contained water from the cement slurry duringcementing can be reduced (that is, the fluid loss may be reduced) andenables the fluidity of the cement slurry to be maintained. When theamount of the fluid loss is great, the fluidity of the cement slurry islost, which makes sufficient cementing difficult.

The fluid loss is a physical property of the oil well cement defined byAmerican Petroleum Institute (API). The testing method for the fluidloss is described in Recommended Practice for Testing Well Cements, APIRecommended Practice 10B-2, April 2013.

The vinyl alcohol polymer used in the additive for oil well cement ofthe present embodiment is the polymer obtained by saponifying thecopolymer of a vinyl ester monomer and a multifunctional monomer. Thevinyl alcohol polymer has the degree of saponification of 70 to 95 mol %and the viscosity-average degree of polymerization of 1000 to 10000. Inthe vinyl alcohol polymer, the particle size is further preferablycontrolled.

The copolymer of the vinyl ester monomer and the multifunctional monomermay further be copolymerized with a monomer other than the vinyl estermonomer, which is copolymerizable with the vinyl ester monomer and themultifunctional monomer, unless it would not impair the effects of thepresent invention.

The vinyl ester monomer may include, for example, vinyl acetate, vinylpropionate, vinyl valerate, vinyl caproate, vinyl laurate, vinylstearate, vinyl benzoate, vinyl pivalate, and the like, or may be amixture thereof. From the viewpoint of the ease of polymerization, vinylacetate is preferable as the vinyl ester monomer.

Examples of a monomer, other than the vinyl ester monomer,copolymerizable with the vinyl ester monomer may include α-olefinmonomers such as ethylene and propylene; (meth)acrylic acid alkyl estermonomers such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl(meth)acrylate, and 2-ethylhexyl (meth)acrylate; unsaturated amidemonomers such as (meth)acrylamide and N-methylol acrylamide; unsaturatedcarboxylic monomers such as (meth)acrylic acid, crotonic acid, maleicacid, itaconic acid, and fumaric acid; alkyl (e.g. methyl, ethyl, andpropyl) ester monomers of unsaturated carboxylic acids; anhydrides ofunsaturated carboxylic acids such as maleic anhydride; salts ofunsaturated carboxylic acids with sodium, potassium, ammonium, and thelike; glycidyl group-containing monomers such as allyl glycidyl etherand glycidyl (meth)acrylate; sulfonic acid group-containing monomerssuch as 2-acrylamide-2-methylpropanesulfonic acid or salts thereof;phosphate group-containing monomers such as acid phosphoxyethyl acrylateand acid phosphoxypropyl methacrylate; and alkyl vinyl ether monomers.

The multifunctional monomer to be copolymerized with the vinyl estermonomer is not particularly limited, and may include a compound that hastwo or more polymerizable unsaturated bonds per molecule. Examplesthereof may include divinyl ether such as propanediol divinyl ether,butanediol divinyl ether, ethylene glycol divinyl ether, diethyleneglycol divinyl ether, triethylene glycol divinyl ether, polyethyleneglycol divinyl ether, propylene glycol divinyl ether, and polypropyleneglycol divinyl ether; and divinylsulfonic acid compounds.

Examples of the multifunctional monomer to be copolymerized with thevinyl ester monomer may also include diene compounds such as pentadiene,hexadiene, heptadiene, octadiene, nonadiene, and decadiene; diallylether compounds such as glycerol diallyl ether, diethylene glycoldiallyl ether, ethylene glycol diallyl ether, triethylene glycol diallylether, polyethylene glycol diallyl ether, trimethylol propane diallylether, and pentaerythritol diallyl ether; triallyl ether compounds suchas allyl methacrylate, glycerol triallyl ether, trimethylol propanetriallyl ether, and pentaerythritol triallyl ether; tetraallyl ethercompounds such as pentaerythritol tetraallyl ether; monomers containingan allyl ester group such as diallyl phthalate, diallyl maleate, diallylitaconate, diallyl terephthalate, and diallyl adipate; monomerscontaining an allylamino group, for example, diallylamine compounds suchas diallylamine and diallylmethylamine, and triallylamine; monomerscontaining an allylammonium group, for example, diallylammonium saltssuch as diallyldimethylammonium chloride; monomers containing two ormore allyl groups such as triallyl isocyanurate, 1,3-diallyl urea,triallyl phosphate, and diallyldisulphide.

Furthermore, examples of the multifunctional monomer to be copolymerizedwith the vinyl ester monomer may include monomers having a (meth)acrylicacid such as ethylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, polyethyleneglycol di(meth)acrylate, propylene glycol di(meth)acrylate,polypropylene glycol di(meth)acrylate, glycerol di(meth)acrylate,glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate,trimethylol propane tri(meth)acrylate, ditrimethylol propanetetra(meth)acrylate, pentaerythritol tetra(meth)acrylate,dipentaerythritol hexa(meth)acrylate, and isocyanuric acidtri(meth)acrylate; monomers having (meth)acrylamide such asN,N′-methylenebis(meth)acrylamide and N,N′-ethylene-bis(meth)acrylamide;divinyl benzene and trivinyl benzene.

Among these multifunctional monomers, triallyl isocyanurate or allylmethacrylate, that have a carbonyl group or an amide group in themolecule, is preferred from the viewpoint of the reactivity with thevinyl ester monomer. In particular, triallyl isocyanurate is preferredfrom the viewpoint of being difficult to decompose in the saponificationreaction and the like.

The amount of copolymerization of the multifunctional monomer in thevinyl alcohol polymer, that is, the structural unit derived from themultifunctional monomer in the vinyl alcohol polymer is preferably 0.001to 1.0 mol % per 100 mol % of the structural unit derived from the vinylester monomer in the vinyl alcohol polymer. The structural unit derivedfrom the multifunctional monomer may preferably be 0.005 to 0.5 mol %,further preferably 0.01 to 0.2 mol %. If the amount of copolymerizationof the multifunctional monomer is 0.001 mol % or more, the effect ofreducing fluid loss may be more sufficiently exhibited. If the amount is1.0 mol % or less, the vinyl alcohol polymer hardly forms excesscrosslinked structures, resulting in good workability, in addition toproviding the effect of reducing fluid loss.

The amount of copolymerization of the multifunctional monomer may becalculated by using ¹³C-NMR. The calculation procedure of the amount ofcopolymerization if the multifunctional monomer is triallyl isocyanuratewill be described as an example.

The vinyl alcohol polymer copolymerized with triallyl isocyanurate iswashed thoroughly with methanol, air dried at 90° C. for 1 hour, andthen dissolved in heavy water to prepare a solution with a concentrationof 10 mass %.

By using 500 MHz ¹³C-NMR (“AV-III HD 500” manufactured by Bruker)equipped with a DCH cryoprobe, ¹³C-NMR spectrum is obtained from theresulting solution at a measurement temperature of 80° C. andaccumulation of 20000 times.

Based on the spectrum obtained, the integral value of peaks (30 to 50ppm) of the backbone methylene groups not adjacent to hydroxy groups inthe vinyl alcohol polymer copolymerized with triallyl isocyanurate isdefined as b and the integral value of peaks (150 to 155 ppm) based oncarbonyl groups in triallyl isocyanurate is defined as a. The amount ofcopolymerization of triallyl isocyanurate X (mol %) in the vinyl alcoholpolymer copolymerized with triallyl isocyanurate is calculated by theformula (1).X=((⅓)a/b)×100  (1)

The polymerization method of the vinyl ester monomer and themultifunctional monomer is not particularly limited, and knownpolymerization methods such as solution polymerization, suspensionpolymerization, and bulk polymerization may be used. Use of a solutionpolymerization method performed in alcohol is preferable, from theviewpoint of the ease of operation and the availability of a commonsolvent with the saponification reaction in the next step. As thealcohol, methanol is particularly preferably used.

The degree of saponification of the vinyl alcohol polymer used in thepresent embodiment is 70 to 95 mol %. If the degree of saponification isless than 70 mol %, the hydrophobicity of the remaining acetyl groups istoo strong, and if the degree of saponification is more than 95 mol %,hydrogen bonds between molecules of the vinyl alcohol polymer are toostrong. In both cases, the affinity with water is lowered, which makesthe effect of reducing fluid loss insufficient.

From the viewpoint of the effect of reducing fluid loss, the degree ofsaponification may preferably be 75 to 90 mol %.

As used herein, the term “degree of saponification” refers to a valuecalculated by measuring according to Japan Industrial Standard JIS K6726, Section 3.5 “Degree of Saponification”.

The saponification reaction is performed by dissolving the copolymer ofthe vinyl ester monomer and the multifunctional monomer in alcohol andadding an alkali catalyst or an acid catalyst thereto. Examples of thealcohol may include methanol, ethanol, and butanol. As mentioned above,use of methanol is particularly preferable.

The concentration of the vinyl ester polymer in alcohol may preferablybe at a concentration of 5 to 80% solids. The alkali catalyst mayinclude, for example, hydroxides of alkali metals such as sodiumhydroxide, potassium hydroxide, sodium methylate, sodium ethylate, andpotassium methylate, and alkali catalysts such as alcoholate. The acidcatalyst may include, for example, aqueous solutions of inorganic acidssuch as hydrochloric acid and sulfuric acid, and organic acids such asp-toluenesulfonic acid. The amount used of these catalysts maypreferably be 0.1 to 100 millimole equivalents based on the structuralunit derived from the vinyl ester monomer. The reaction temperatureduring saponification may preferably be in the range of 10 to 70° C.,more preferably in the range of 30 to 50° C. The reaction time maypreferably be 1 to 10 hours.

The viscosity-average degree of polymerization of the vinyl alcoholpolymer is 1000 to 10000, preferably 1500 to 6000, more preferably 2000to 5000. Too low viscosity-average degree of polymerization makes theeffect of reducing fluid loss insufficient, and too highviscosity-average degree of polymerization lowers fluidity due to anincrease in the viscosity of the cement slurry.

The term “viscosity-average degree of polymerization” refers to a valuecalculated by the following formula (2) from the intrinsic viscosity [η](g/dL) measured at 30° C. with an Oswald viscometer using ion exchangewater as a solvent.log(P)=1.613×log([η]×104/8.29)  (2)wherein, P represents the viscosity-average degree of polymerization.

The content of the vinyl alcohol polymer having a particle size of 75 μmor less may preferably be 30 mass % or less, more preferably 25 mass %or less, further preferably 15 mass % or less. By adjusting the contentof the vinyl alcohol polymer having a particle size of 75 μm or less to30 mass % or less, the dissolution rate of the vinyl alcohol polymer inthe cement slurry does not become too fast and the deterioration offluid loss reducing performance may be inhibited.

The content of the vinyl alcohol polymer having a particle size of 500μm or more may preferably be 10 mass % or less, more preferably 8 mass %or less, further preferably 5 mass % or less. By adjusting the contentof the vinyl alcohol polymer having a particle size of 500 μm or more to10 mass % or less, the vinyl alcohol polymer is less likely to become adefected portion upon curing of the cement and thus the reduction in thestrength of a cured product of cement is less likely to occur.

Cement slurry according to an embodiment of the present inventioncontains a certain amount of the additive for oil well cement describedabove.

The method of adding the vinyl alcohol polymer into the cement slurry isnot particularly limited, and conventional methods such as a method ofmixing with a dried cement composition in advance and a method of mixingin the preparation of a cement slurry are employed.

The content of the vinyl alcohol polymer in the cement slurry is 0.01 to30% bwoc, preferably 0.05 to 10% bwoc, more preferably 0.1 to 5% bwoc.Note that the abbreviation “bwoc” stands for “by weight of cement,” andrefers to the weight of the additive in dry form to be added to a cementcomposition, only based on the solids content of the cement.

EXAMPLES

Hereinafter, the present invention will be described in detail withreference to Examples, but the present invention is not limited thereto.Unless stated otherwise, the terms “parts” and “%” mean “parts by mass”and “mass %,” respectively.

Preparation of Vinyl Alcohol Polymer Example 1

In a polymerization tank equipped with a reflux condenser, a droppingfunnel, and a stirrer, 100 parts by mass of vinyl acetate, 0.01 parts bymass of triallyl isocyanurate, 17.0 parts by mass of methanol, and 0.07parts by mass of Peroyl NPP (Nippon Oil & Fats Co., Ltd.) were placed,and polymerization was performed at the boiling point for 5 hours whilestirring under a nitrogen stream. When the conversion rate of vinylacetate reached 50%, polymerization was stopped and unreacted vinylacetate was removed outside the polymerization system by a conventionalmethod. A methanol solution of the vinyl acetate polymer was obtained,and the viscosity-average degree of polymerization was 5900.

To the methanol solution of the vinyl acetate polymer obtained above, amethanol solution of sodium hydroxide (0.007 in terms of moles of sodiumhydroxide relative to the structural unit derived from vinyl acetate)was added, and a saponification reaction was performed at 45° C. for 90minutes. The reaction solution obtained was dried by heating, and avinyl alcohol polymer of Example 1 was obtained. The vinyl alcoholpolymer had the degree of saponification of 80.0 mol %.

The dried vinyl alcohol polymer was subjected to primary grinding by agrinder, and then sieved by using a sieve having an opening of 500 μm.The on-sieve products were subjected to grinding again by a grinder andmixed well with previously obtained the under-sieve products. In theresulted vinyl alcohol polymer, the particle size was adjusted such thatthe proportion of particles of 500 μm or more was 0%, and the proportionof particles of 75 μm or less was 12.0%.

Note that in the primary grinding, the time until the proportion ofparticles of 500 μm or more reached 30% or less, and in the grinding ofthe on-sieve products, the proportion of particles of 500 μm or morereached 5% or less were evaluated by a pre-test in advance. In theExamples, grinding was performed based on each time evaluated in thepre-test.

Example 2

By using the methanol solution of the vinyl acetate polymer obtained inExample 1, a vinyl alcohol polymer was obtained in the same manner as inExample 1, except that the degree of saponification of the vinyl alcoholpolymer was changed to 88.2 mol %.

The particle size of the dried vinyl alcohol polymer was adjusted usinga grinder in the same manner as in Example 1 such that the proportion ofparticles having a particle size of 500 μm or more was 0.2%, and theproportion of particles having a particle size of 75 μm or less was8.5%.

Example 3

In a polymerization tank equipped with a reflux condenser, a droppingfunnel, and a stirrer, 100 parts by mass of vinyl acetate, 0.036 partsby mass of triallyl isocyanurate, 22.1 parts by mass of methanol, and0.06 parts by mass of Peroyl NPP (Nippon Oil & Fats Co., Ltd.) wereplaced, and polymerization was performed at the boiling point for 5hours while stirring under a nitrogen stream. When the conversion rateof vinyl acetate reached 50%, polymerization was stopped and unreactedvinyl acetate was removed outside the polymerization system by aconventional method. A methanol solution of the vinyl acetate polymerhaving the viscosity-average degree of polymerization of 4600 wasobtained.

To the methanol solution of the vinyl acetate polymer obtained above, amethanol solution of sodium hydroxide (0.007 in terms of moles of sodiumhydroxide relative to the structural unit derived from vinyl acetate)was added, and a saponification reaction was performed at 45° C. for 90minutes. The resulted reaction solution was dried by heating, and avinyl alcohol polymer of Example 3 was obtained. The degree ofsaponification was 79.7 mol %.

The particle size of the dried vinyl alcohol polymer was adjusted usinga grinder in the same manner as in Example 1 to obtain a vinyl alcoholpolymer in which the proportion of particles having a particle size of500 μm or more was 0.1%, and the proportion of particles having aparticle size of 75 μm or less was 9.8%.

Example 4

By using a methanol solution of the vinyl acetate polymer obtained inExample 3, a vinyl alcohol polymer was obtained in the same manner asExample 3.

The dried vinyl alcohol polymer was subjected to primary grinding by agrinder, and then sieved by using a sieve having an opening of 500 μm.The on-sieve products were subjected to grinding again by a grinder andmixed well with previously obtained the under-sieve products. In theresulted vinyl alcohol polymer, the particle size was adjusted such thatthe proportion of particles of 500 μm or more was 0.1%, and theproportion of particles of 75 μm or less was 32.2%.

Example 5

By using a methanol solution of the vinyl acetate polymer obtained inExample 3, a vinyl alcohol polymer was obtained in the same manner as inExample 3, except that the degree of saponification of the vinyl alcoholpolymer was changed to 87.6%.

Example 6

In a polymerization tank equipped with a reflux condenser, a droppingfunnel, and a stirrer, 100 parts by mass of vinyl acetate, 0.013 partsby mass of allyl methacrylate, 22.1 parts by mass of methanol, and 0.04parts by mass of Peroyl NPP (Nippon Oil & Fats Co., Ltd.) were placed,and polymerization was performed at the boiling point for 5 hours whilestirring under a nitrogen stream. When the conversion rate of vinylacetate reached 56%, polymerization was stopped and unreacted vinylacetate was removed outside the polymerization system by a conventionalmethod. A methanol solution of the vinyl acetate polymer was obtained.The viscosity-average degree of polymerization was 3900.

To the methanol solution of the vinyl acetate polymer obtained above, amethanol solution of sodium hydroxide (0.007 in terms of moles of sodiumhydroxide relative to the structural unit derived from vinyl acetate)was added, and a saponification reaction was performed at 45° C. for 90minutes. The resulted reaction solution was dried by heating, and avinyl alcohol polymer of Example 6 was obtained. The degree ofsaponification of 80.1 mol %.

The particle size of the dried vinyl alcohol polymer was adjusted usinga grinder in the same manner as in Example 1 such that the proportion ofparticles having a particle size of 500 μm or more was 0%, and theproportion of particles having a particle size of 75 μm or less was9.9%.

Comparative Examples 1 to 4

As Comparative Example 1, PVA was not added. Measurement of fluid losswas performed on Comparative Example 1.

PVA of Comparative Example 2 was prepared in the same manner as inExample 1, except that the multifunctional monomer was eliminated fromExample 1.

By using a methanol solution of the vinyl acetate polymer obtained inExample 1, a vinyl alcohol polymer of Comparative Example 3 was obtainedin the same manner as in Example 1, except that the degree ofsaponification of the vinyl alcohol polymer was changed to 99 mol %.

PVA according to Comparative Example 4 was prepared in the same manneras in Example 1, except that the multifunctional monomer was eliminatedand the amount of methanol placed was reduced to 5.0 parts.

[Calculation of Viscosity-Average Degree of Polymerization of VinylAlcohol Polymer]

With respect to each vinyl alcohol polymer according to Examples 1 to 6and Comparative Examples 2 to 4 obtained above, the intrinsic viscosity[η] (g/dL) was measured, and the viscosity-average degree ofpolymerization was calculated by using the above formula (2).

[Amount of Copolymerization of Multifunctional Monomer of Vinyl AlcoholPolymer]

With respect to each vinyl alcohol polymer according to Examples 1 to 5obtained above, the amount of copolymerization of the multifunctionalmonomer was calculated by using the following method.

The vinyl alcohol polymer copolymerized with triallyl isocyanurate waswashed thoroughly with methanol, air dried at 90° C. for 1 hour, andthen dissolved in heavy water to prepare a solution with a concentrationof 10 mass %.

By using 500 MHz ¹³C-NMR (“AV-III HD 500” manufactured by Bruker)equipped with a DCH cryoprobe, ¹³C-NMR spectrum was obtained from theresulting solution at a measurement temperature of 80° C. andaccumulation of 20000 times.

Based on the spectrum obtained, the integral value of peaks (30 to 50ppm) of the backbone methylene groups not adjacent to hydroxy groups inthe vinyl alcohol polymer was defined as b and the integral value ofpeaks (150 to 155 ppm) based on carbonyl groups in triallyl isocyanuratewas defined as a. The amount of copolymerization of triallylisocyanurate X (mol %) in the vinyl alcohol polymer copolymerized withtriallyl isocyanurate was calculated by the following formula (1).X=((⅓)a/b)×100  (1)[Measurement of Fluid Loss]

The effect of reducing fluid loss of the obtained vinyl alcohol polymerof each of the Examples and Comparative Example 3 and PVA of ComparativeExamples 1, 2 and 4 was measured by using a fluid loss test equipmentModel 7120 manufactured by Chandler Engineering in accordance with thefluid loss evaluation method of the standards of American PetroleumInstitute (API) 10B-2 (April, 2013). The oil well cement was tested byusing Type G and the formulation with no addition of fly ash and noaddition of bentonite under the conditions of a cement slurry density of1900 kg/m³ and a slurry yield of 0.758 m³/ton. The amount of the vinylalcohol polymer added was 0.25% bwoc at an evaluation temperature of 20°C., 0.4% bwoc at 40° C., 0.6% bwoc at 60° C., 0.8% bwoc at 80° C., and0.8% bwoc at 100° C. As a curing retardant for cement, 0.2% bwoc oflignin sulfonate was added under the condition of 40° C., and 0.4% bwocof lignin sulfonate was added under the condition of 60° C. or more.

The results obtained are shown in Table 1. In the Table, “TAIC” of themultifunctional monomer represents triallyl isocyanurate, and “AM”represents allyl methacrylate.

TABLE 1 Example 1 2 3 4 5 6 Vinyl acetate polymer Polymerizationformulation Vinyl acetate [Parts by mass] 100 100 100 100 100 100Multifunctional Type TAIC TAIC TAIC TAIC TAIC AM monomer [Parts by mass]0.010 0.010 0.036 0.036 0.036 0.020 Methanol [Parts by mass] 17.0 17.022.1 22.1 22.1 17.0 Vinyl acetate [%] 50 50 50 50 50 56 conversion rateVinyl acetate polymer Physical property Viscosity-average degree 5,9005,900 4,600 4,600 4,600 3,900 of polymerization Vinyl alcohol polymerPhysical property Amount of copolymerization [mol %] 0.0062 0.00620.0230 0.0230 0.0230 — of multifunctional monomer Viscosity-averagedegree 3,400 3,300 2,900 2,900 2,900 2,080 of polymerization Degree ofsaponification [mol %] 80.0 88.2 79.7 79.7 87.6 80.1 Particle size 500μm or more [Mass %] 0.0 0.2 0.1 0.1 0.1 0.0 75 μm or less [Mass %] 12.08.5 9.8 32.2 9.8 9.9 Fluid loss test Test temperature [cc] 12 14 12 1812 22 20° C. Test temperature [cc] 18 18 14 23 14 77 40° C. Testtemperature [cc] 16 27 14 120 16 196 60° C. Test temperature [cc] 22 8028 180 24 350 80° C. Test temperature [cc] 170 230 102 330 88 — 100° C.Comparative Example 1 2 3 4 Vinyl acetate polymer Polymerizationformulation Vinyl acetate [Parts by mass] — 100 100 100 MultifunctionalType — — TAIC — monomer [Parts by mass] — 0.00 0.01 0.00 Methanol [Partsby mass] — 17.0 17.0 5.0 Vinyl acetate [%] — 50 50 40 conversion rateVinyl acetate polymer Physical property Viscosity-average degree — 2,8005,900 4,900 of polymerization Vinyl alcohol polymer Physical propertyAmount of copolymerization [mol %] — — 0.0062 — of multifunctionalmonomer Viscosity-average degree — 2,200 3,300 3,500 of polymerizationDegree of saponification [mol %] — 79.7 99.0 80.0 Particle size 500 μmor more [Mass %] — 0.0 0.4 0.0 75 μm or less [Mass %] — 8.8 7.4 13.1Fluid loss test Test temperature [cc] 910 14 550 10 20° C. Testtemperature [cc] — 26 — 14 40° C. Test temperature [cc] — 120 — 48 60°C. Test temperature [cc] — — — 380 80° C. Test temperature [cc] — — — —100° C.

It was found from Table 1 that the additive for oil well cementcontaining the vinyl alcohol polymer obtained in the present inventionis capable of significantly reducing fluid loss of the oil well cementeven at a high temperature.

It was found from the comparison between Examples and ComparativeExamples 2 and 4 that when no multifunctional monomer was copolymerized,the effect of reducing fluid loss at a high temperature becomesinsufficient. It was also found from the comparison between Examples andComparative Example 3 that even when the multifunctional monomer wascopolymerized, too high a degree of saponification does not cause theeffect of reducing fluid loss to be exhibited.

The present invention may include the following embodiments.

[1] An additive for oil well cement, comprising a vinyl alcohol polymer,wherein the vinyl alcohol polymer is a saponified product of a copolymerof a vinyl ester monomer and a multifunctional monomer, and the vinylalcohol polymer has a degree of saponification of 70 to 95 mol % and aviscosity-average degree of polymerization of 1000 to 10000.[2] The additive for oil well cement according to [1], wherein themultifunctional monomer includes a carbonyl group or an amide group.[3] The additive for oil well cement according to [1] or [2], whereinthe multifunctional monomer is triallyl isocyanurate.[4] The additive for oil well cement according to any one of [1] to [3],wherein a structural unit derived from the multifunctional monomer inthe vinyl alcohol polymer may be 0.001 to 1.0 mol % per 100 mol % of astructural unit derived from the vinyl ester monomer.[5] The additive for oil well cement according to any one of [1] to [4],wherein a content of the vinyl alcohol polymer having a particle size of75 μm or less is 30 mass % or less, and a content of the vinyl alcoholpolymer having a particle size of 500 μm or more is 10 mass % or less.[6] A cement slurry containing 0.01 to 30% bwoc of the additive for oilwell cement according to any one of [1] to [5].

The invention claimed is:
 1. A vinyl alcohol polymer, wherein the vinylalcohol polymer is a saponified product of a copolymer of a vinylacetate monomer and a multifunctional monomer, the vinyl alcohol polymerhas a degree of saponification of 70 to 95 mol% and a viscosity-averagedegree of polymerization of 1000 to 10000, a structural unit derivedfrom the multifunctional monomer in the vinyl alcohol polymer is 0.001to 0.0230 mol % per 100 mol % of a structural unit derived from thevinyl ester monomer, and the multifunctional monomer includes two ormore allyl groups.
 2. The vinyl alcohol polymer according to claim 1,wherein the multifunctional monomer further includes a carbonyl group oran amide group.
 3. The vinyl alcohol polymer according to claim 1,wherein the multifunctional monomer is triallyl isocyanurate.
 4. Thevinyl alcohol polymer according to claim 1, wherein a content of thevinyl alcohol polymer having a particle size of 75 μm or less is 30 mass% or less, and a content of the vinyl alcohol polymer having a particlesize of 500 μm or more is 10 mass % or less.
 5. A cement slurrycomprising 0.01 to 30% bwoc of the vinyl alcohol polymer according toclaim 1.